Mercerizing agent



aienied June 10, 194i.

runnonnro AGENT poration of Delaware No Drawing.

Application May 20, 1939,

Serial No. 274,788

(Cl. 8l.27)

8 Claims.

The present invention relates to a new and improved process andcomposition for improving and accelerating the wetting properties ofalkaline aqueous media, such as strong alkaline solutions used formercerizing cellulosic fibers. It is known that ordinary soaps, namely,the alkali metal salts of high molecular weight fatty acids, possesswetting properties in distilled water. In strong alkaline solutions,however, such compounds have very little or no wetting properties.

An object of this invention is to produce alkaline aqueous media forimproving and accelerating the mercerizing efiect of alkalies uponcellulosic fibers such as cotton and similar textile materials. Afurther object of the invention is to produce an aqueous bath which isrelatively concentrated in alkaline reacting substances, such ascaustic, and yet possesses marked wetting, penetrating and dispersingcharacteristics. A specific object of the invention is to producerelatively concentrated solutions of alkali metal hydroxides whichpossess the property of accelerating the mercerizing effect of strongalkaline hydroxides upon cellulosic fibers.

The objects of the invention are accomplished by adding to stronglyalkaline aqueous media a particular type of wetting agent comprisingsoluble N-alkylated aromatic amine di-sulfonates.

Also the soluble salt, preferably the alkali metal salt such as thesodium and potassium salts, may be formed in the mercerizing media byadding thereto the N-alkylated aromatic amine di-sulionic acids. 1 havefound that these di-sulfonates possess excellent wetting properties inthe presence of strong alkalies, such as used in mercerizing baths. a v

The di-sulfonates employed in the present invention may be representedby the following general formula:

wherein R represents an aromatic nucleus of the benzene, biphenyl andnaphthalene type; R1 represents a hydrogen or an alkyl radicalcontaining N-ethyl aniline di-sodium-sulfonate N-n-propyl anilinedi-sodium-sulfonate N-isopropyl aniline di-sodium-sulionate N-n-butylaniline di-sodium-sulionate N-tertiarybutyl aniline di-sodium-sulfonateN-isobutyl aniline di-sodium-sulfonate N-amyl anilinedi-sodium-sulfonate N-n-dibutyl aniline di-sodium-sulfonate N-n-dibutylaminotoluene di-sodium-sulfonate N-tertiaryamyl p-amino-biphenyldi-sodium-sulfonate N-n-propyl )p-amino-biphenyl di-sodium-sulfon-Mixtures of the above products may be used, for

example, N-amyl and N-diamyl o-amino biphenyl di-sodium-sulfonates, andN-n-butyl and N -n-dibutyl o-amino biphenyl di-sodium-sulfonates, aswell as mixtures of the other N-alkyl and N-dialkyl aromatic aminedi-alkalimetal-sulfonates.

Within the classes of compounds herein disclosed, the group ofN-alkylated o-amino-biphenyl (ii-sodium sulfonates is extremelyeffective for use in mercerizing baths and their superior efiectivenessin this respect is unique.

The following examples illustrate some of the methods that may be usedto prepare the herein described N-alkylated aromatic amine di-sulfonicacids and their salts.

EXAMPLE I Five tenths mols of ortho-amino biphenyl, grams of butylalcohol (solvent) and 0.5 mol of n-butyl bromide were refluxed for fourhours at about 117 C. and the reaction mixture was then heated todistill oil the solvent. The residue was washed with 25%; aqueouscaustic solution to liberate the free base and then distilled, underreduced pressure to recover the N-alkylated amino biphenyls. Forty-twoand a half grams of N-nbutyl ortho-amino biphenyl was distilled from thereaction mixture at a temperature of 128-135 C. I

at 2 mm. pressure and 51.6 grams of N-n-dibutyl ortho-amino biphenyldistilled at 135-160 C. at 2 mm. pressure. Either of these N-alkylo-aminobiphenyls or the mixture may be sulfonated by the followingmethod.

Twelve grams of the N-dibutyl ortho-amino diphenyl, 50 grams of drycarbon tetrachloride (sol vent) and 11.5 grams of chlorosulfonic acidwere refluxed together at 75-80 C. until the last trace.

of HCl was liberated. The reaction mixture was diluted with water andthe carbon tetrachloride removed. The water solution was then dried onsteam plates to a white powder. By neutralizing the acid with sodiumhydroxide, the N-n-dibutylortho-amino-biphenyl di-sodium-sulfonate isobtained.

EXAMPLE 11 One mol of ortho-amino biphenyl hydrochloride, three mols oftertiary amyl alcohol and one gram of iodine (catalyst) were heated in arotary autoclave for five hours at 175-180 C. under 450 to 480 poundspressure. The reaction product was then made alkaline with sodiumhydroxide, filtered and washed with water until neutral. The reactionproducts were then distilled under reduced pressure and theN-tertiary-amyl-orthoamino biphenyl distilled over between 140-150" C.at one mm. pressure.

One mol of a N-tertiary-amyl-ortho-amino-biphenyl, two mols ofchlorosulfonic acid and 1,000 grams of carbon tetrachloride wererefluxed for five hours. The carbon tetrachloride (solvent) wasseparated ofi and the reaction product dissolved in alcohol andneutralized with 420 c. c. of 25% aqueous sodium hydroxide. Theneutralized alcoholic solution was filtered and then dried. TheN-tertiary-amyl-ortho-amino biphenyl di-sulfonic acid, in particularlyquantitative yield, was recovered by evaporating the alcohol therefrom.Upon neutralization of the acid with caustic or sodium carbonate, thecorresponding di-sulfonate is obtained.

Exmmm One mol of ortho-amino-diphenyl hydrochloride, three mols oftertiary butyl alcohol, and one gram of iodine (catalyst) were heated ina rotary autoclave for five hours at 125-135 C. under 600 to 700 poundspressure. The reaction product was then made alkaline with sodiumhydroxide, filtered, and washed with water until neutral. Benzene wasthen added to dissolve the reaction product from the remainder of thereacted constitutents. The benzene solution was distilled to remove thebenzene and the residue was distilled under reduced pressure. TheN-tertiary butyl ortho-amino biphenyl distilled between 135-140 C. at 1mm, pressure.

One-tenth mol of the N-tertiary butyl orthoamino biphenyl, 0.2 mol ofchlorosulfonic acid and 100 grams of carbon tetrachloride (solvent) weremixed together at about 20-30 C. and refluxed for five hours. The carbontetrachloride was separated on and the reaction product dissolved inalcohol and neutralized with 36 .c. c. of 25% aqueous sodium hydroxide.After cooling the neutralized solution, it was filtered and thealcoholic solution dried. The N-tertiary butylortho-amino biphenyldE-sulfonic-acid was recovered therefrom by evaporating the alcohol.Upon neutralization of the acid with an alkali, the correspondingdi-sulfonate is obtained.

EXAMPLE IV Di-n-butyl aniline was sulfonated by the procedure used inthe preceding example to prepare the di-n-butyl anilinedi-sodium-sulfonate. In general, the N-alkylated aromatic amine may beprepared by reacting the hydrochoride of the aromatic amine with thevarious alcohols under a pressure of 400 to 600 pounds at a temperatureof about 150-210" C. If desired, a small amount of iodine may be used tocatalyze the reaction. After neutralizing the charge, the excessunreacted alcohol is recovered by distillation and the unreacted amineas well as the N-alkylated amine are separated by fractionaldistillation under reduced pressure. The solfonation is preferablycarried out in a solvent such as carbon tetrachloride ortetrachlor-ethane, and two mols of chlorosulfonic acid is used for eachmol of the N-alkylated aromatic amine.

As pointed out hereinbefore, the salts of dissulfonated N-alkylatedaromatic amines are particularly adapted for use in mercerizing bathsbecause they retain their wetting properties in the presence of strongalkaline solutions. In general, these sulfonated products are used inconcentrations ranging from 0.2% to 3% but preferably concentrationswithin the 0.8% to 1.5% are used. The concentration or alkali,

such as sodium hydroxide, in the mercerizing bath may vary over therange commercially used for mercerizing cotton fabrics. In general thealkali content of the bath will vary from 12 to 40%. The hereindescribed di-sulfonated compounds may be added to the bath in the formof the salt but if desired they may be added in the form of the freeacid. In the latter case,

however, the acid will be converted into the pletely wet, that is, tosink below the surface of the solution.

TABLE I Wetting test-String method Wettina time in seconds of 1%solution of Test Material the "material" in an aquoous 20% N a0isolution Hours 1 Control l8 2.... 'N-n-butyl o-arninobipheuyl(ii-sodiumsulfonalc 3i 3..." N-n-propyl o-aminoblphcnyl dlSOdllllll-Sultanate... 62 .4 N-n-amyl o-aminobiphenyl di-smllumsulfonate... m 5N-terliary butyl o-annnoblphonyl d1- smlium-sulfonute v 82 6 N-tortiaryamyl o-arninobipbenyl d1- SOsllUllI-SulfOllfitB (-0 7N-di-u-hutylanilinedi-sodinm-suljonatev 45 8 N-octyl o-aminobiphcnyldi-sndium-sul l'onate r 2m 9 N-dimcthyl aniline monosodium sullonate. +8

ing the amount of shrinkage at 15 second intervals. The apparatusconsisted of a 50 ml. burette whose graduations cover a length of 56.5centimeters, a metal guide to center and hold the yarn and a 2 gramstainless steel weight fitted with a hook. In making the test, theburette is filled with the mercerizing solution containing the newwetting agent (1% solution by weight of the wetting agent in an aqueous20% sodium hydroxide solution). The temperature of the'solution isadjusted to 20 C. The end of a single strand of yarn (70/2 soft, creamHimalaya cotton) is attached to the 2 gram weight and the strand is thensuspended in the burette with the top of the weight standing at the 50mm. mark. The shrinkage of the yarn is noted at 15 second intervals.

Since the treatment of cotton fibers with stron alkaline solutions suchas a strong aqueous solution of sodium hydroxide causes a shrinkage ofthe fiber, the amount of this shrinkage in a given period of timerepresents the efficiency or effectiveness of the mercerizing bath. Byplacing the strand of yarn in the above burette which contains themercerizing agent, the emciency of the bath can be ascertained by notingthe height to which the weight rises in a given period of time. Thefollowing data obtained by the above test illustrate the efficiency ofrepresentative examples of the herein described N- allwlated aryl aminedi-sulfonates when incorporated in a mercerizing bath.

' TABLE I1 Percent shrink e in aqueous 20% NapH Percent containing 1% ofan N-aikyi o-aminoshrinkage in biphenyl di-sodium sulfonates in whichSeconds aqueous 20% the alkyl radical is- NaOH n-Propyl n-Butyl n-AmylTert.amyl

- The mercerizing efficiency of an aqueous 20% sodium hydroinde solutioncontaining one per cent. of one of the above N-alkyl ortho-aminobiphenyl di-sodium-sulfonates as compared to the aqueous 20% sodiumhydroxide solution alone is clearly demonstrated by the above data. In30 seconds the sodium hydroxide solution alone caused less than 1%shrinkage in the length of the strand, whereas the mercerizing bathcontaining one of the above mentioned wetting agents produced ashrinkage of about 13% in the same time interval. Even after 240seconds, the mercerizing bath without the wetting agent produced only a5.3% shrinkage. In addition, the merceriration effected by the hereindescribed products is uniform and the fabric can be dyed evenly. Theseimprovements may be accom- Plished with cellulosic fibers that have notbeen subjected to the boiling out or cleansing process that is normallyused to remove waxes and greases from the fibers before passing them tothe mercerizing bath. By using the improved mercerizing bath hereindescribed, I not only shorten the time normally used to mercerizecellulosic fibers but I can eliminate some of the preliminary cleaningsteps that are normally applied to the fibers before passing them to themercerizing bath.

The herein described alkaline aqueous media may be employed in admixturewith other addition agents for example alcohols such as secondary-amylalcohol and tertiarybutyl alcohol; phenols such as cresylic acid; Turkeyred oils and the like.

While the described invention is preferably employed in themercerization of cotton fibers, fabrics and yarns it may be used in anyart or process where it is desirable to have a strong alkaline mediumhaving wetting, penetrating and dispersing properties.

As illustrated by the foregoing data, the herein described classes ofwater-soluble N-alkyiated aromatic amine di-sulfonates are characterizedby their high degree of'wetting, penetrating and dispersing propertiesin alkaline solutions such as strong aqueous solutions of sodiumhydroxide. These properties of the foregoing di-sulfonated products makeit possible to obtain rapid and uniform mercerization, thereby effectinga substantial economy in the continuous type of mercerizing process.

Inasmuch as the above specification comprises preferred embodiments ofthe invention, it is to be understood that the invention is not limitedthereto and that variations and changes may be made without departingsubstantially from the invention as defined in the appended claims.

I claim:

1. .An alkaline mercerizing solution containing as a wetting agent an N-alkylated aromatic amine di-sulfonate having the following generalformula:

wherein R represents an aromatic radical selected from the groupconsisting of benzene, biphenyl and naphthalene radicals, R1 representsa hydrogen or an alkyl radical containing from two to six carbon atoms,Me represents an alkali metal, and the term alkyP' represents an alkylradical containing from two to six carbon atoms.

2. A strongly alkaline medium of improved wetting properties comprisingan aqueous alkali metal hydroxide solution of an N -alkylated aromaticamine di-sodium-sulfonate having the following general formula: I

R: alkylI l'R=(S 0am), wherein R represents an aromatic radical selectedfrom the group consisting of benzene, biphenyl and naphthalene radicals,R1 represents a hydrogen or an alkyl radical containing from two to sixcarbon atoms, and the term alkyl represents an alkyl radical containingfrom two to six carbon atoms.

3. In the process of producing mercerized cotton materials, the stepwhich comprises suba sodiumhydnoxide mercerizing bath containing as awetting agent a small amount of a watersoluble N-alkylated aromaticamine di-sulfonate having the following general formula:

R1 alkyll IR=(S onus wherein R represents an aromatic radical selectedfrom the group consisting of benzene, biphenyl and naphthalene radicals,R1 represents a hydrogen or an alkyl radical containing -from two to sixcarbon atoms, Me represents an alkali metal, and the term alkyrepresents an alkyl radical containing from two to six carbon atoms.

4. A strongly alkaline medium of improved wetting properties comprisingan aqueous alkali metal hydroxide solution of mercerizing strength,characterized by containing an N-alkylated aromatic amine di -sulfonichaving the following general formula:

wherein R represents a biphenyl radical, R1 I represents a hydrogen or'an alkyi radical containing from two to six carbon atoms, Me representsan alkali metal, and the term alkyl represents an alkyl radicalcontaining from two to six carbon atoms.

5. An alkaline mercerizing solution containing as a wetting agent anN-alkylated aromatic amine di-sulfonate having the following generalformula: 4

1 Alkyl-NR=(S 03MB): wherein R represents a biphenyl radical, R1reprepresents a hydrogen or an alkyl radical containing from two to sixcarbon atoms, Me represents an alkali metal, and. the term alkylrepresents an alkyl radical containing from two to six carbon atoms.

6. A wetting agent capable of increasing the wetting properties ofaqueous solutions of alkali metal hydroxides, which comprises an N-alkylortho-amino biphenyl disulfonate wherein thealkyl group contains fromtwo to six carbon atoms. 7. A new composition of matter comprising anN-alkylated biphenylamine disulfonate having the general formula:

Aikyl NR=( s olMe wherein R represents a biphenyl radical, R1 representsa hydrogen or an alkyl radical containing from two to six carbon atoms,Me represents an alkali metal, and the term alkyl represents an alkylradical containing from two to six carbon atoms, said compounds'beingsoluble in aqueous alkaline solutions and possessing wetting properties.

8. A new composition of matter comprising an N-dialkylated biphenylaminedisulfonate having the following general formula: 1

wherein R represents a biphenyl radical, R1 and R: represent butylradicals and Me represents an alkali metal, said compounds being solublein CERTIFICATE OF CORRECTION. Patent No. 2,215,162. June 10, l9hl.

ROBERT L. SIBLEY.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,first column, line #0, in the equation, for "R read -R page 2, firstcolumn, line 55-5h, for "constitutents" read constituents-; and secondcolumn, line 15, for "solfonation" read -sulfonation; line 26, for "or"read of-; line L t, for "boundle" read bundle; and that the said LettersPatent should be read with this correction therein that the same mayconform to the record of the case in the Patent Ofilice.

Signed'and sealed this 15th day of July, A. D. 19in.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents.

v CERTIFICATE OF CORRECTION. Patent No. 2,215,162. June 10, 19in.

ROBERT L. SIBLEY.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,first column, line 14.0, in the equation, for "R read R page 2, firstcolumn, line 55-5 for "constitutents" read -c-onstituents-; and secondcolumn, line 15, for "solfonation" read sulfonation-; line 26, for "or"read 0f; line L t, for "boundle" read -bundle--; and that the saidLetters Patent should be read with this correction therein that the samemay conform to the record of the case in the Patent Office.

Signedand sealed this 15th day of July, A. D. 19in.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents.

